The present invention is directed to ink compositions and ink jet printing processes. More specifically, the present invention is directed to aqueous ink compositions particularly suitable for the production of high quality images on print substrates. One embodiment of the present invention is directed to an ink composition comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block. Another embodiment of the present invention is directed to a set of inks for printing multicolor images in an ink jet printer, said ink set comprising (1) a first ink having a first color and comprising water and a first colorant; and (2) a second ink having a second color different from the first color and comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the second ink is printed adjacent to, on top of, or underneath the first ink on a print substrate. Yet another embodiment of the present invention is directed to a multicolor ink jet printing process which comprises: (1) incorporating into an ink jet printer a first ink having a first color and comprising water and a first colorant; (2) incorporating into the ink jet printer a second ink having a second color different from the first color and comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block; (3) causing droplets of the first ink to be ejected in an imagewise pattern onto a substrate; and (4) causing droplets of the second ink to be ejected in an imagewise pattern onto the substrate, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the second ink is printed adjacent to, on top of, or underneath the first ink on the substrate.
Ink jet printing is a non-impact printing method which produces droplets of ink that are deposited on a print substrate in response to electronic digital data signals. Ink jet systems generally are of two types: continuous stream and drop-on-demand. In continuous stream ink jet systems, ink is ejected in a continuous stream under pressure through at least one orifice or nozzle. The stream of ink is periodically perturbed by pressure regulation in accordance with digital signals, causing it to break up into droplets at a fixed distance from the nozzle. At the break-up point, the charged ink droplets pass through an electrical field which adjusts the trajectory of each ink droplet to direct it to a gutter for ink circulation or to a specific location on a print substrate to produce an image. In a drop-on-demand system, an ink droplet is expelled from a nozzle directly onto a print substrate in accordance with digital data signals. Generally, a droplet is not formed or expelled unless it is to be placed on a print substrate.
Drop-on-demand systems are simpler than continuous stream systems since they do not require ink recovery, charging, or deflection. There are three types of drop-on-demand ink jet systems. One type of drop-on-demand system has an ink-filled channel or passageway having a nozzle on one end and a piezoelectric transducer near the other end to produce pressure pulses according to digital data signals. Multiple ink nozzles are used to deliver ink droplets onto a print substrate in an imagewise fashion. Several printheads and inks are used in a multicolor piezoelectric ink jet printing system. High resolution images can be obtained with this system. Examples of this system include the Epson 600, 800, and 1200 Ink Jet printers.
Another type of drop-on-demand ink jet printing system is called acoustic ink jet printing, which can be operated at high frequency and high resolution. Acoustic ink jet printing uses a focused acoustic beam formed with a spherical lens illuminated by a plane wave of sound created by a piezoelectric transducer. The focused beam reflected from a surface exerts a pressure onto the surface of the liquid ink, resulting in ejection of small droplets of ink onto a print substrate. An array of nozzles and corresponding transducers are used in an acoustic ink jet printing process to produce images on a print substrate in an imagewise fashion. Different types and configurations of acoustic printheads and substrate arrangements are possible. In a multicolor ink jet printing process, several acoustic ink jet printheads are used to deliver different inks onto a print substrate. Aqueous inks can be used in this drop-on-demand acoustic ink jet printing system. Examples of acoustic ink jet printing systems are disclosed in, for example K. A. Krause, xe2x80x9cFocusing Ink Jet Head,xe2x80x9d IBM Technical Disclosure Bulletin, Vol 16, No. 4, September 1973, pp. 1168-1170, and in, for example, U.S. Pat. Nos. 4,308,547, 4,697,195, 5,028,937, 5,041,849, 4,751,529, 4,751,530, 4,751,534, 4,801,953, and 4,797,693, the disclosures of each of which are totally incorporated herein by reference. The use of focused acoustic beams to eject droplets of controlled diameter and velocity from a free-liquid surface is also described in J. Appl. Phys., vol. 65, no. 9 (May 1, 1989) and references therein, the disclosure of which is totally incorporated herein by reference.
Another type of drop-on-demand printing system is thermal ink jet printing. Thermal or bubble jet drop-on-demand ink jet printers have found broad applications as output for personal computers in the office and in the home. In thermal ink jet printing processes, the printhead typically comprises one or more ink jet ejectors, as disclosed in, for example, U.S. Pat. Nos. 4,601,777, 4,532,530, 4,412,224, 4,410,899, 4,251,824, 4,532,530, 4,601,777, 4,840,674, 5,145,518, 5,281,261, and 5,531,818, the disclosures of each of which are totally incorporated herein by reference. Each ejector includes a channel communicating with an ink supply chamber, or manifold, at one end and an opening at the opposite end, referred to as a nozzle. A thermal energy generator, usually a resistor, is located in each of the channels at a predetermined distance from the nozzles. The resistors are individually addressed with a current pulse to vaporize the ink momentarily within the respective channel to form a bubble that expels an ink droplet. As the bubble grows, the ink rapidly bulges from the nozzle and is momentarily contained by the surface tension of the ink as a meniscus. This phenomenon is temporary, and the ink is quickly propelled toward a print substrate. As the bubble begins to collapse, the ink still in the channel between the nozzle and the bubble starts to move towards the collapsing bubble, causing a volumetric contraction of the ink at the nozzle and resulting in the separation from the nozzle of the bulging ink as a droplet. The acceleration of the ink out of the nozzle while the bubble is growing provides the momentum and velocity for propelling the ink droplet in a substantially straight direction toward a print substrate, such as a piece of paper, transparency, textile, or the like. Some important properties of the ink in this context include desirable viscosity and surface tension, adequate drop velocity, good latency and frequency response, minimum heater deposits (kogation), and no soft threshold voltage problems. Because the droplet of ink is emitted only when the resistor is actuated, thermal ink jet printing is a drop-on-demand system.
In a drop-on-demand ink jet printing apparatus, the printhead typically comprises a linear array of ejectors, and the printhead (with or without partition) is moved relative to the surface of the print substrate, either by moving the print substrate relative to a stationary printhead, or vice versa, or both. In some apparatus, a relatively small printhead moves across a print substrate numerous times in swaths (i.e., multiple passes) to print a desired image. In this instance, the desired image is produced completely on a print substrate in several swaths before the substrate is advanced. This type of printing is called multi-pass (multiple pass) or checkerboard ink jet printing. In checkerboard ink jet printing (or multiple pass), the printhead passes over the print substrate and provides ink at desired locations (for example, printing only even or odd numbered dots in a swath). On one or more subsequent passes, the remaining dots in the image are printed before the print substrate is advanced. Multiple ink jet printheads and ink cartridges can be used to produce multiple color images on a print substrate. Alternatively, a printhead (partial width printhead or partitioned printhead) can be partitioned into several sections (for example, three small sections including cyan, magenta, and yellow inks, or four small sections including cyan, magenta, yellow, and black inks) and equipped with different ink chambers, ink storage media, and inks in a multicolor ink jet printing system. These multicolor systems are commonly employed in desktop ink jet printers, including thermal ink jet printers and piezoelectric ink jet printers. They produce good multicolor images on print substrates such as plain papers and transparencies, but at a slower printing speed. Slightly higher printing speed can be achieved, however, by increasing ink jetting frequency and printhead sweeping rate as well as by using multiple printheads (without partition) and inks.
The ink jet printing apparatus can also employ a printhead comprising two or more printheads butted together to cover a larger width of the print substrate (butted printhead). This type of partial width printhead has more ink nozzles per printhead and can deliver more ink in each swath across the print substrate. In the multi-pass (multiple passes) or checkerboard ink jet printing process a faster ink jet printing process can be carried out. Multicolor ink jet printing processes can use several butted ink jet printheads (e.g. for black, cyan, magenta, and yellow inks) in an ink jet printer to produce multicolored images on substrates at a faster rate than processes using several regular single printheads without butting (unbutted printheads).
Alternatively, a stationary ink jet printhead that consists of an array of ejectors and extends the full width of a print substrate (full width array printhead) can pass ink down the print substrate to give full page images, in what is known as a xe2x80x9cfull width arrayxe2x80x9d ink jet printer. When the printhead and the print substrate are moved relative to each other, imagewise digital data is used to activate the thermal energy generators or resistors selectively in the printhead over time so that the desired image can be created quickly on the print substrate in a single pass mode. The full width array printhead is generally preferred to be in a stationary position while the print substrate is continuously moving to receive inks as it passes through the printhead or printheads. The full width array printhead or printheads can also, however, be moved across the print substrate if desired. In a multicolor ink jet printing process, several full width array printheads, including cyan, magenta, yellow, and black printheads, as well as other optional printheads and their corresponding inks, can be used to provide different colored images on the print substrate at a high speed. Fast ink jet printing can be achieved by using the full width array printheads.
In a multicolor ink jet printing process, several inks can be printed on a print substrate. In some instances two different inks can be printed next to each other. Intercolor bleed can occur if the inks are not dried properly or if the printing process is too fast for the ink set. Undesired ink mixing on a print substrate, especially on the surface of a plain paper, can cause severely distorted images near the border of two inks. After ink drying, the border of the two inks shows irregular structure with poor edge sharpness (or raggedness) because of the invasion of one ink into the other. The bleed images are not desirable and can be detected easily by eyes. This phenomenon is called intercolor bleed or color bleed. Intercolor bleed is particularly noticeable when a darker ink (such as a black ink) and a lighter ink (such as a yellow ink, a cyan ink, magenta ink, or the like) are printed next to each other, because of high contrast between the two colors. Intercolor bleed can also occur when two color inks are printed next to each other (for example, a yellow ink next to a magenta ink, a yellow ink next to a cyan ink, a magenta ink next to a cyan ink, or the like). The severity of the intercolor bleed generally is affected by ink type and composition, absorption rate of the printed substrate, printhead design, ink drop mass, ink dot size, and method and speed of printing. There is a need to reduce or minimize intercolor bleed and dry time and to produce high quality multicolor ink jet images on print substrates, including plain and coated papers, transparencies, textiles, and other desired substrates.
While known compositions and processes are suitable for their intended purposes, a need remains for improved ink compositions. In addition, a need remains for improved ink compositions suitable for use in ink jet printing processes. Further, a need remains for ink sets for ink jet printing that enable the generation of multicolored images with reduced intercolor bleed. Additionally, a need remains for ink compositions that enable improved print quality with sharp line edges. There is also a need for ink compositions with reduced drying time. In addition, there is a need for ink compositions that exhibit desirable surface tension values. Further, there is a need for ink compositions that generate images with improved uniformity of solid image areas. Additionally, there is a need for ink compositions with desirable latency values in ink jet printers. A need also remains for ink compositions that improve ink jet printhead maintainability. In addition, a need remains for multicolor ink jet printing processes that enable desirable print quality and uniform solid area images.
The present invention is directed to an ink composition comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block. Another embodiment of the present invention is directed to a set of inks for printing multicolor images in an ink jet printer, said ink set comprising (1) a first ink having a first color and comprising water and a first colorant; and (2) a second ink having a second color different from the first color and comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the second ink is printed adjacent to, on top of, or underneath the first ink on a print substrate. Yet another embodiment of the present invention is directed to a multicolor ink jet printing process which comprises: (1) incorporating into an ink jet printer a first ink having a first color and comprising water and a first colorant; (2) incorporating into the ink jet printer a second ink having a second color different from the first color and comprising water, a colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block; (3) causing droplets of the first ink to be ejected in an imagewise pattern onto a substrate; and (4) causing droplets of the second ink to be ejected in an imagewise pattern onto the substrate, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the second ink is printed adjacent to, on top of, or underneath the first ink on the substrate.
The ink compositions of the present invention comprise an aqueous liquid medium, a colorant, and a block copolymer. The aqueous liquid medium can consist solely of water, or can also include water soluble or water miscible organic components such as humectants, cosolvents, and the like. Many useful known humectants and/or cosolvents are suitable for use in the inks for the present invention. Some suitable humectants and cosolvents include, but are not limited to, glycol derivatives, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly(ethylene-co-propylene) glycol, and the like, as well as their reaction products with alkylene oxides, including ethylene oxide and propylene oxide; alkyl ethers of glycol derivatives, such as alkyl ethers (alkyl group containing from about 1 to 25 carbon atoms) of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, poly ethylene glycol, polypropylene glycol, poly(ethylene-co-propylene) glycol, and the like; triol derivatives containing from about 3 to about 40 carbon atoms, including glycerine, trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol, and the like, as well as their reaction products with alkylene oxides, including ethylene oxide, propylene oxide, and mixtures thereof; diols containing from about 2 to about 40 carbon atoms, such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 2,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), and the like, as well as their reaction products with alkylene oxides, including ethylene oxide and propylene oxide in any desirable molar ratio to form materials with a wide range of molecular weights; sulfoxide derivatives containing from about 2 to about 40 carbon atoms, including dialkylsulfoxides (symmetric and asymmetric sulfoxides) such as dimethylsulfoxide, methylethylsulfoxide, alkylphenyl sulfoxides, and the like; sulfone derivatives (symmetric and asymmetric sulfones) containing from about 2 to about 40 carbon atoms, including dialkyl sulfones such as dimethysulfone, methylethylsulfone, diethylsulfone, ethylpropylsulfone, dipropylsulfone, propylbutylsulfone, dibutylsulfone, sulfolane (tetramethylenesulfone, a cyclic sulfone), methylsulfolane, dimethylsulfolane, and the like, alkyl phenyl sulfones, such as methylphenylsulfone, ethylphenyl sulfone, and the like; amides with from about 2 to about 40 carbon atoms, such as N-alkylamides, N,N-dialkyl amides, N,N-alkyl phenyl amides, 2-pyrrolidinone (a cyclic amide), N-methylpyrrolidinone (a cyclic amide), N-cyclohexylpyrrolidinone, N,N-dimethyl-p-toluamide (aromatic), N,N-dimethyl-o-toluamide, N,N-diethyl-m-toluamide, and the like; ethers, such as alkyl ether derivatives of various alcohols, ether derivatives of triols and diols, including butylcarbitol, hexylcarbitol, triolethers, alkyl ethers of polyethyleneglycols, alkyl ethers of polypropyleneglycols, phenyl ethers of polyethyleneglycols, phenyl ethers of polypropyleneglycols, alkyl ethers of phenylpolyethyleneglycols, alkyl ethers of phenylpolypropyleneglycols, and the like; urea and urea derivatives; inner salts such as betaine, and the like; thio (sulfur) derivatives (or isomers) of the aforementioned materials (humectants), including thioethyleneglycol, thiodiethyleneglycol, trithio- or dithio-diethyleneglycol, and the like; hydroxyamide derivatives, including acetylethanolamine, acetylpropanolamine, propylcarboxyethanolamine, propylcarboxypropanolamine, and the like; reaction products of aforementioned materials (humectants) with alkylene oxides; and mixtures thereof.
Further examples of suitable humectants are disclosed in, for example, U.S. Pat. Nos. 5,281,261, 5,531,818, 5,693,129, 4,840,674, 5,356,464, copending application U.S. Ser. No. 08/782,237, and copending application U.S. Ser. No. 08/876,41, the disclosures of each of which are totally incorporated herein by reference. For example, U.S. Pat. No. 5,693,129 discloses the use of hydroxyamide derivatives, mercaptoamide derivatives, hydroxythioamide derivatives, mercaptothioamide derivatives, and oxyalkylene (alkyleneoxide) reaction products of the above said derivatives as anticurl agents for ink jet ink compositions. These materials and other known anti-curl agents, including those disclosed in, for example, U.S. Pat. No. 5,356,464 can be employed in the inks for the present invention to provide both anticurl and antibleed properties for the production of multicolor images. Furthermore, ink compositions for the present invention further comprising some of the materials disclosed in U.S. Pat. No. 5,693,129 and copending application U.S. Ser. No. 08/782,237 can be used in a high resolution ink jet printing process to provide long ink latency and high frequency response. The inks for the present invention, in some embodiments, will have a reduced tendency to clog the printhead nozzles or resist smooth ink flow, and will exhibit less frequency of ink spitting and printhead wiping for maintenance. Furthermore, the ink compositions for the present invention can be used with regular printheads, partitioned printheads, partial width printheads, and full width array printheads in ink jet printing processes. The ability of the ink compositions for the present invention to be jetted at high frequency (because of high frequency response, typically 3 KiloHertz or greater) allows one to print multicolor ink jet images at high speed, especially when full width array ink jet printheads are used. A printing speed of 50 copies per minutes for the production of multicolor images can be achieved using a set of full width array printheads (e.g. black, cyan, magenta, and yellow). The print substrates can optionally be heated at any stage of the printing process, including before, during, and after the printing process as well as combinations thereof.
Humectants, if present, are in the ink in any desired or effective amount, typically up to about 45 percent by weight of the ink, preferably up to about 40 percent by weight of the ink, and more preferably from about 5 to about 35 percent by weight of the ink, although the amount can be outside of these ranges.
Ink compositions of the present invention can also be prepared with low viscosity. Low molecular weight materials are preferred in the inks. Some examples of additional useful ink ingredients are disclosed in, for example, U.S. Pat. Nos. 5,281,261, 5,531,818, and 5,693,129, the disclosures of each of which are totally incorporated herein by reference. Ink compositions for the present invention with low viscosity can allow fast ink jetting and refill in multicolor ink jet printing processes with inks of the present invention. The viscosity of the ink composition is usually less than about 20 centipoise (at room temperature, i.e., about 25xc2x0 C.), preferably from about 1 to about 10 centipoise, and more preferably from about 1 to about 5 centipoise.
The ink compositions of the present invention further contain a colorant. The colorant can be a pigment, a dye, or a mixture thereof. A pigment colorant is one that is substantially insoluble in the ink aqueous medium. The pigment can be selected from the suitable colorants listed in the Color Index, published jointly by American Association of Textile Chemist and Colorists (AATCC) and The Society of Dyers and Colorists in Bradford, England; BUYER""S GUIDE for Textile Chemist and Colorist, published by AATCC, and the like. The pigment can be present in the inks either with or without a dispersing agent. For example, pigment particles such as those modified chemically to possess water ionizable functional groups (either negatively or positively charged), such as carboxylate, sulfonate, phosphonate, phosphate, or ammonium groups, are stable in an aqueous ink and do not necessarily require a dispersing agent. Unlike many commercially available unmodified pigments, which rely primarily on external polymeric dispersants for needed stability in aqueous inks, the chemically modified pigments have the functional groups attached directly to the pigment particle surfaces via covalent bonds. The water ionizable functional groups can stabilize the pigment particles in the aqueous ink medium and provide needed stability without undesired pigment precipitation or coagulation. If needed, however, a pigment dispersant can also be used in conjunction with the chemically modified pigment (or surface modified pigment) to improve the stability of the ink. Some examples of chemically modified pigments are disclosed in, for example, U.S. Pat. No. 5,281,261, the disclosure of which is totally incorporated herein by reference; also suitable are commercial carbon black dispersions such as Cabojet(copyright) 200, Cabojet(copyright) 300 (surface modified pigment), colored pigment dispersions, available from Cabot Chemical Co., the Bonjet(copyright) carbon black dispersions from Orient Chemical Company of Japan, other commercially available surface modified pigments (e.g. carbon black and color pigments), and the like. Pigment particles which are not chemically modified preferably are present with at least a dispersing agent (or dispersant) to stabilize the particles in an aqueous ink. The pigment stabilizing or dispersing agent can be anionic, cationic, or nonionic.
Pigments can be of any desired color, such as black, cyan, magenta, yellow, red, blue, green, brown, or the like, as well as mixtures thereof. It is preferred that the pigment particles in an ink jet ink composition have the same or similar color so there is no interference or impairment of the desired color of the final ink. Examples of suitable pigments in the ink jet ink compositions include, but are not limited to, various carbon blacks such as channel blacks; furnace blacks; lamp blacks; Raven(copyright) carbon blacks including Raven(copyright) 5250, Raven(copyright) 5750, Raven(copyright) 3500 and other similar carbon black products available from Columbia Company; carbon blacks including Regal(copyright) 330, Black Pearl(copyright) L, Black Pearl(copyright) 1300, and other similar carbon black products available from Cabot Corporation; Degussa carbon blacks such as Color Black(copyright) series, Special Black(copyright) series, Printtex(copyright) series and Derussol(copyright) carbon black dispersions available from Degussa Company; Cabojet(copyright) series carbon black dispersions including Cabojet(copyright) 200, Cabojet(copyright) 300, Cabojet(copyright) IJX 157, Cabojet(copyright) IJX 164, and the like from Cabot corporation; Lavanyl(copyright) carbon black dispersions from Bayer Company, Special Black(copyright) carbon black dispersions from BASF Co.; Hostafine(copyright) series pigment dispersions such as Hostafine(copyright) Yellow GR (Pigment 13), Hostafine(copyright) Yellow (Pigment 83), Hostafine(copyright) Red FRLL (Pigment Red 9), Hostafine(copyright) Rubine F6B (Pigment 184), Hostafine(copyright) Blue 2G (Pigment Blue 15:3), Hostafine(copyright) Black T (Pigment Black 7, carbon black), and Hostafine(copyright) Black TS (Pigment Black 7), available from Hoechst/Celanese Corporation; Normandy Magenta RD-2400 (Paul Uhlich); Paliogen Violet 5100 (BASF); Paliogen(copyright) Violet 5890 (BASF) Permanent Violet VT2645 (Paul Uhlich); Heliogen Green L8730 (BASF); Argyle Green XP-111-S (Paul Uhlich); Brilliant Green Toner GR 0991 (Paul Uhlich); Heliogen(copyright) Blue L6900; L7020 (BASF), Heliogen(copyright) Blue D6840, D7080 (BASF); Sudan Blue OS (BASF); PV Fast Blue B2G01 (Hoechst/Celanese); Irgalite Blue BCA (Ciba-Geigy); Paliogen(copyright) Blue 6470 (BASF); Sudan III (Matheson, Coleman, Bell); Sudan II (Matheson, Coleman, Bell); Sudan IV (Matheson, Coleman, Bell); Sudan Orange G (Aldrich); Sudan Orange 220 (BASF); Paliogen(copyright) Orange 3040 (BASF); Ortho Orange OR 2673 (Paul Uhlich); Paliogen(copyright) Yellow 152, 1560 (BASF); Lithol Fast Yellow 0991 K (BASF); Paliotol Yellow 1840 (BASF); Novoperm(copyright) Yellow FG 1 (Hoechst/Celanese); Permanent Yellow YE 0305 (Paul Uhlich); Lumogen Yellow D0790 (BASF); Suco-Gelb L1250 (BASF); Suco-Yellow D1355 (BASF); Hostaperm(copyright) Pink E (Hoechst/Celanese), Fanal Pink D4830 (BASF); Cinquasia Magenta (DuPont); Lithol Scarlet D3700 (BASF); Toluidine Red (Aldrich); Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada); E. D. Toluidine Red (Aldrich); Lithol Rubine Toner (Paul Uhlich); Lithol Scarlet 4440 (BASF); Bon Red C (Dominion Color Company); Royal Brilliant Red RD-8192 (Paul Uhlich); Oracet Pink RF (Ciba-Geigy); Pigment Red 122 from Toyo Ink of Japan; Paliogen(copyright) Red 3871 K (BASF); Paliogen(copyright) Red 3340 (BASF); Lithol Fast Scarlet L4300 (BASF); and mixtures thereof. Many useful pigments can also be found in the Color Index, published jointly by American Association of Textile Chemist and Colorists (AATCC) and The Society of Dyers and Colorists in Bradford, England.
Pigment colorants can be present in the ink in any effective amount. Typically the pigment is present in an amount of from about 0.1 to about 15 percent by weight of the ink, and preferably from about 1 to about 10 percent by weight of the ink, although the amount can be outside of these ranges.
Preferably, the pigment particle size is as small as possible to enable a stable colloidal suspension of the particles in the liquid medium with good color strength, and to prevent clogging of the ink channels or nozzle openings when the ink is used in an ink jet printer. Preferred average particle sizes or diameters are generally from about 0.001 to about 3 microns, although the particle sizes can be outside of these ranges. A more preferred pigment particle size distribution is one wherein particles having at least 50 percent of the particles being below 0.3 micron, with no particles being greater than 3.0 microns (measured on, for example, a Hodaka CAPA 700 Particle Size Analyzer, a Malvern particle size analyzer, a Model BI-90 Brookhaven Instruments particle size analyzer, or the like). More preferably, the average pigment particle size includes particles having at least 70 percent of the particles being below 0.3 micron, with no particles being greater than 1.2 microns. Pigment particle sizes can, however, be outside of these ranges provided that they do not cause undesired clogging and maintenance problems.
In some embodiments of the present invention, the pigment can be dispersed in the ink with one or more dispersants (dispersing agents) or stabilizing agents. The stabilizing agents can be anionic, cationic, or nonionic. Some pigment stabilizing agents have both hydrophilic (comprising ionic groups which are capable of ionizing in water or water compatible groups) and hydrophobic (affinity for pigments) moieties. Suitable stabilizing agents include, but are not limited to, anionic dispersants, such as polymers and random copolymers of styrene sulfonate salts (such as Na+, Li+, K+, Cs+, Rb+, substituted and unsubstituted ammonium cations, and the like), unsubstituted and substituted (such as alkyl, alkoxy, substituted naphthalene derivatives, and the like) naphthalene sulfonate salts (such as Na+, Li+, K+, Cs+, Rb+, substituted and unsubstituted ammonium cations, and the like) with an aldehyde derivative, such as unsubstituted alkyl aldehyde derivatives, including formaldehyde, acetaldehyde, propylaldehyde, and the like, as well as mixtures thereof. Examples of such stabilizing agents include, but are not limited to, commercial products such as Versa(copyright) 4, Versa(copyright) 7, Versa(copyright) 77 (National Starch and Chemical Co.); Lomar(copyright) D (Diamond Shamrock Chemical Co.); Daxad(copyright) 19, Daxad(copyright) K (W. R. Grace and Co.); Tamol(copyright) SN (Rohm and Haas); and the like. Other useful anionic stabilizing agents include polymers or random copolymers of styrene and an acrylic acid salt, styrene and a methacrylic acid salt, styrene and a maleic acid salt, block copolymers comprising acrylates or methacrylates, and the like, as well as mixtures thereof.
Nonionic pigment stabilizing agents (or dispersing agents or dispersants) or surfactants can also be used in inks for the present invention, such as ethoxylated monoalkyl or dialkyl phenols, including Igepal(copyright) CA and CO series materials (Rhone-Poulenc Co., such as Igepal(copyright) CA-630, CO-630, and the like); Surfynol(copyright) series materials from Air Products and Chemicals Co.; and Triton(copyright) series materials (Union Carbide Company). These nonionic surfactants or dispersants can be used alone or in combination with anionic or cationic dispersants.
The ratio of pigment to stabilizing agent by weight typically is from about 1:0.01 to about 1:4, preferably from about 1:0.1 to about 1:2, and more preferably from about 1:0.10 to about 1:1.5, although the ratio can be outside of these ranges.
The ratio of naphthalene substituent to aldehyde in the aforementioned anionic stabilizing agents typically is about 1:1, although this ratio can be different depending on the stoichiometry of the feed stock and reaction condition, and can readily be adjusted to obtain a dispersant having a desired molecular weight and the desired ratio of naphthalene substituent to aldehyde. The weight average molecular weight of the pigment stabilizing agent is generally less than about 50,000, preferably less than about 25,000, and more preferably less than about 10,000, although the weight average molecular weight can be outside of these ranges. The pigment dispersion preferably contains enough dispersant to stabilize the pigment particles in water, but not so much as to affect adversely properties of the dispersion and ink such as viscosity, stability, and optical density.
Dye colorants are those colorants that are soluble in the aqueous liquid vehicle. The dye can be selected from the suitable colorants listed in the Color Index, published jointly by American Association of Textile Chemist and Colorists (AATCC) and The Society of Dyers and Colorists in Bradford, England; BUYER""S GUIDE for Textile Chemist and Colorist, published by AATCC, and the like. Any suitable dye or mixture of dyes that is compatible with the other ink ingredients can be used. Water soluble or water dispersible anionic dyes, direct dyes, reactive dyes, and cationic dyes can be selected. Examples of suitable dyes include, but are not limited to, Food dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, and the like; FD and C dyes; Acid Black dyes (No. 1, 7, 9, 24, 26, 48, 52, 58, 60, 61, 63, 92, 107, 109, 118, 119, 131, 140, 155, 156, 172, 194, and the like); Acid Red dyes (No. 1, 8, 32, 35, 37, 52, 57, 92, 115, 119, 154, 249, 254, 256, and the like); Acid Blue dyes (No. 1, 7, 9, 25, 40, 45, 62, 78, 80, 92, 102, 104, 113, 117, 127, 158, 175, 183, 193, 209, and the like); Acid Yellow dyes (No. 3, 7, 17, 19, 23, 25, 29, 38, 42, 49, 59, 61, 72, 73, 114, 128, 151, and the like); Direct Black dyes (No. 4, 14, 17, 22, 27, 38, 51, 112, 117, 154, 168, and the like); Direct Blue dyes (No. 1, 6, 8, 14, 15, 25, 71, 76, 78, 80, 86, 90, 106, 108, 123, 163, 165, 199, 226, and the like); Direct Red dyes (No. 1, 2, 16, 23, 24, 28, 39, 62, 72, 236, 337, and the like); Direct Yellow dyes (No. 4, 11, 12, 27, 28, 33, 34, 39, 50, 58, 86, 100, 106, 107, 118, 127, 132, 142, 157, and the like); anthraquinone dyes; monoazo dyes; disazo dyes; phthalocyanine derivatives, including various phthalocyanine sulfonate salts; aza (18) annulenes; Formazan copper complexes; triphenodioxazines; Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A; Pontamine; Caro direct Turquoise FBL Supra Conc. (Direct Blue 199), available from Carolina Color and Chemical; Special Fast Turquoise 8GL Liquid (Direct Blue 86), available from Mobay Chemical; Intrabond Liquid Turquoise GLL (Direct Blue 86), available from Crompton and Knowles; Cibracron Brilliant Red 38-A (Reactive Red 4), available from Aldrich Chemical; Reactive Dyes (e.g. Reactive Black 5, Reactive Blue 2, Reactive Blue 4, Reactive Blue 15, Reactive Orange 16, Reactive Red 2, Reactive Red 4, Reactive Yellow 2, and Reactive Yellow 81) from Aldrich Chemical Co.; Reactive Red 180 and its hydrolyzed form from Mitsubishi Chemical Co. of Japan; Drimarene Brilliant Red X-2B (Reactive Red 56), available from Pylam, Inc.; Levafix Brilliant Red E-4B, available from Mobay Chemical; Levafix Brilliant Red E-6BA, available from Mobay Chemical; Procion Red H8B (Reactive Red 31), available from ICI of America (Zeneca Co.); Pylam Certified DandC Red #28 (Acid Red 92), available from Pylam; Direct Brilliant Pink B Ground Crude, available from Crompton and Knowles; Cartasol Yellow GTF Presscake, available from Sandoz, Inc.; Tartrazine Extra Conc. (FDandC Yellow #5, Acid Yellow 23), available from Sandoz; Carodirect Yellow RL (Direct Yellow 86), available from Carolina Color and Chemical; Cartasol Yellow GTF Liquid Special 110, available from Sandoz, Inc.; DandC Yellow #10 (Acid Yellow 3), available from Tricon; Yellow Shade 16948, available from Tricon; Basacid Black X34, available from BASF; Carta Black 2GT, available from Sandoz, Inc.; Neozapon Red 492, available from BASF; Orasol Red G available from Ciba-Geigy; Direct Brilliant Pink B (Crompton-Knolls); Aizen Spilon Red C-BH (Hodogaya Chemical Company); Kayanol Red 3BL (Nippon Kayaku Company); Levanol Brilliant Red 3BW (Mobay Chemical Company); Levaderm Lemon Yellow (Mobay Chemical Company); Spirit Fast Yellow 3G; Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company); Sirius Supra Yellow GD 167; Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy); Orasol Black RL (Ciba-Geigy); Orasol Black RLP (Ciba-Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT (Sandoz); Pyrazol Black BG (ICI); Morfast Black Conc A (Morton-Thiokol); Diazol Black RN Quad (ICI); Orasol Blue GN (Ciba-Geigy); Savinyl Blue GLS (Sandoz); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid Blue 750 (BASF); Bernacid Red, available from Berncolors, Poughkeepsie, N.Y.; Pontamine Brilliant Bond Blue; Berncolor Acid Yellow 34; Telon Fast Yellow 4GL-175; BASF Basacid Black SE 0228; the Pro-Jet(copyright) series of dyes available from Zeneca Co., including Pro-Jet(copyright) Yellow I (Direct Yellow 86), Pro-Jet(copyright) Magenta I (Acid Red 249), Pro-Jet(copyright) Cyan I (Direct Blue 199), Pro-Jet(copyright) Black I (Direct Black 168), Pro-Jet(copyright) Yellow 1-G (Direct Yellow 132), and Pro-Jet(copyright) waterfast dyes; Aminyl Brilliant Red F-B, available from Sumitomo Chemical Company (Japan); the Duasyn(copyright) line of xe2x80x9csalt-freexe2x80x9d dyes available from Hoechst/Celanese, such as Duasyn(copyright) Direct Black HEF-SF (Direct Black 168), Duasyn(copyright) Black RL-SF (Reactive Black 31), Duasyn(copyright) Direct Yellow 6G-SF VP216 (Direct Yellow 157), Duasyn(copyright) Brilliant Yellow GL-SF VP220 (Reactive Yellow 37), Duasyn(copyright) Acid Yellow XX-SF LP413 (Acid Yellow 23), Duasyn(copyright) Brilliant Red F3B-SF VP218 (Reactive Red 180), Duasyn(copyright) Rhodamine B-SF VP353 (Acid Red 52), Duasyn(copyright) Direct Turquoise Blue FRL-SF VP368 (Direct Blue 199), and Duasyn(copyright) Acid Blue AE-SF VP344 (Acid Blue 9); Dispersed Dyes; various Reactive dyes, including Reactive Black dyes, Reactive Blue dyes, Reactive Red dyes, and Reactive Yellow dyes; and the like; as well as mixtures thereof.
A dye colorant is present in the ink in any effective amount to provide desired color and optical density. Typically, the dye is present in an amount from about 0.01 to about 15 percent by weight of the ink, preferably from about 0.1 to about 10 percent by weight of the ink, more preferably from about 1 to about 8 percent by weight of the ink, and even more preferably from about 1 to about 5 percent by weight of the ink, although the amount can be outside of these ranges. A mixture of dyes in any desired proportion can also be employed to obtain a specific shade or hue.
The ink compositions of the present invention also contain an ABCBxe2x80x2Axe2x80x2 or BACAxe2x80x2Bxe2x80x2 block copolymer wherein the A and Axe2x80x2 blocks contain one or more ethylene oxide repeat monomer units, the B and Bxe2x80x2 blocks contain one or more propylene oxide repeat monomer units, and the C block contains one or more repeat monomer units of a dialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane. Optionally, the A or B block and the C block can be separated by an optional spacer group S. Optionally, the C block and the Bxe2x80x2 or Axe2x80x2 blocks can be separated by an optional spacer group Sxe2x80x2. Accordingly, the block copolymers of the present invention can also be represented as ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymers, wherein S and Sxe2x80x2 are optional spacer groups.
The ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 and BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymers suitable for the inks of the present invention have a linear structure (linear polymer backbone), and are to be distinguished from grafted or branched dimethylsiloxane copolymers.
A and Axe2x80x2 are each blocks comprising one or more repeat monomer units of ethylene oxide. The A and Axe2x80x2 blocks can be either the same as each other or different from each other in terms of chain length. A and Axe2x80x2 preferably each have from 1 to about 10,000 repeat ethylene oxide units, although the number of repeat ethylene oxide units can be outside of this range.
B and Bxe2x80x2 are each blocks comprising one or more repeat monomer units of propylene oxide. The B and Bxe2x80x2 blocks can be either the same as each other or different from each other in terms of chain length. B and Bxe2x80x2 preferably each have from 1 to about 10,000 repeat propylene oxide units, although the number of repeat propylene oxide units can be outside of this range.
C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, a diarylsiloxane, or mixtures thereof. The alkyl or aryl groups on the alkylsiloxane, dialkylsiloxane, alkyl aryl siloxane, and/or diarylsiloxane repeat monomer units typically have from 1 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range. Particularly preferred repeat monomers for the C block include dimethyl siloxane, methyl ethyl siloxane, diethyl siloxane, methylphenyl siloxane, diphenyl siloxane, and the like. C preferably is selected so that the number of repeat alkylsiloxane, dialkylsiloxane, alkyl aryl siloxane, and/or diarylsiloxane units in the ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer is from 1 to about 5,000, although the number of repeat siloxane units can be outside of this range.
S is an optional spacer group between the A or B blocks and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the B or Axe2x80x2 blocks. In an ABSCSBxe2x80x2Axe2x80x2 block copolymer, when S is absent, the B block is directly bonded to the C block, and in a BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer, when S is absent, the A block is directly bonded to the C block. In an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 block copolymer, when Sxe2x80x2 is absent, the Bxe2x80x2 block is directly bonded to the C block, and in a BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer, when Sxe2x80x2 is absent, the Axe2x80x2 block is directly bonded to the C block. S and Sxe2x80x2 each, independently of the other, can be (but are not limited to) alkylene groups, alkylene oxide groups, alkylsilyl groups, dialkylsilyl groups, alkylarylsilyl groups, diarylsilyl groups, propylenylalkylsilyl groups, propylenyldialkylsilyl groups, propylenylalkylarylsilyl groups, propylenyidiarylsilyl groups, alkylsiloxy groups, dialkylsiloxy groups, alkylarylsiloxy groups, diarylsiloxy groups, propyleneoxyalkylsilyl groups, propylenylalkylsiloxy groups, propyleneoxydialkylsilyl groups, propylenyidialkylsiloxy groups, propyleneoxyalkylarylsilyl groups, propylenylalkylarylsiloxy groups, propyleneoxydiarylsilyl groups, propylenyldiarylsiloxy groups, heteroatoms, or mixtures thereof. Examples of suitable alkylene S and Sxe2x80x2 groups include those with from 1 to about 10 carbon atoms, such as those of the formula xe2x80x94(CH2)txe2x80x94 wherein t is an integer of from 1 to about 10, such as methylene (xe2x80x94CH2xe2x80x94), ethylene (xe2x80x94CH2CH2xe2x80x94), propylene (xe2x80x94CH2CH2CH2xe2x80x94), and the like. Examples of suitable alkylene oxide S and Sxe2x80x2 groups include those with from 1 to about 10 carbon atoms, such as methylene oxide (xe2x80x94CH2Oxe2x80x94 or xe2x80x94OCH2xe2x80x94), ethylene oxide (xe2x80x94CH2CH2Oxe2x80x94 or xe2x80x94OCH2CH2xe2x80x94), propylene oxide (xe2x80x94CH2CH2CH2Oxe2x80x94 or xe2x80x94OCH2CH2CH2xe2x80x94), and the like. Examples of suitable alkylsilyl S and Sxe2x80x2 groups, dialkylsilyl S and Sxe2x80x2 groups, alkylarylsilyl S and Sxe2x80x2 groups, diarylsilyl S and Sxe2x80x2 groups, propylenylalkylsilyl S and Sxe2x80x2 groups, propylenyldialkylsilyl S and Sxe2x80x2 groups, propylenylalkylarylsilyl S and Sxe2x80x2 groups, and propylenyldiarylsilyl S and Sxe2x80x2 groups include those wherein the alkyl moieties have from 1 to about 10 carbon atoms and the aryl moieties have from 6 to about 20 carbon atoms, such as dimethylsilyl (xe2x80x94Si(CH3)2xe2x80x94), methylethylsilyl (xe2x80x94Si(CH3)(C2H5)xe2x80x94), methylphenylsilyl (xe2x80x94Si(CH3)(C6H5)xe2x80x94), diphenylsilyl (xe2x80x94Si(C6H5)2xe2x80x94), dimethylpropylenylsilyl (xe2x80x94C3H6xe2x80x94Si(CH3)2xe2x80x94 or xe2x80x94Si(CH3)2xe2x80x94C3H6xe2x80x94), and the like. Examples of suitable alkylsiloxy S and Sxe2x80x2 groups, dialkylsiloxy S and Sxe2x80x2 groups, alkylarylsiloxy S and Sxe2x80x2 groups, diarylsiloxy S and Sxe2x80x2 groups, propyleneoxyalkylsilyl S and Sxe2x80x2 groups, propylenylalkylsiloxy S and Sxe2x80x2 groups, propyleneoxydialkylsilyl S and Sxe2x80x2 groups, propylenyldialkylsiloxy S and Sxe2x80x2 groups, propyleneoxyalkylarylsilyl S and Sxe2x80x2 groups, propylenylalkylarylsiloxy S and Sxe2x80x2 groups, propyleneoxydiarylsilyl S and Sxe2x80x2 groups, and propylenyldiarylsiloxy S and Sxe2x80x2 groups include those wherein the alkyl moieties have from 1 to about 10 carbon atoms and the aryl moieties have from 6 to about 20 carbon atoms, such as dimethylsiloxy (xe2x80x94Si(CH3)2Oxe2x80x94), methylethylsiloxy (xe2x80x94Si(CH3)(C2H5)Oxe2x80x94), methylphenylsiloxy (xe2x80x94Si(CH3)(C6H5)Oxe2x80x94), diphenylsiloxy (xe2x80x94Si(C6H5)2Oxe2x80x94), dimethylpropylenylsiloxy (xe2x80x94C3H6xe2x80x94Si(CH3)2Oxe2x80x94 or xe2x80x94Si(CH3)2xe2x80x94C3H6Oxe2x80x94 or xe2x80x94OC3H6xe2x80x94Si(CH3)2xe2x80x94 or xe2x80x94OSi(CH3)2xe2x80x94C3H6xe2x80x94), and the like. Examples of suitable S and Sxe2x80x2 heteroatoms include oxygen, nitrogen, phosphorus, sulfur, silicon, and the like, as well as mixtures thereof. Two or more of the aforementioned suitable S and Sxe2x80x2 groups can also be combined to provide a spacer group; for example, a single spacer group S or Sxe2x80x2 can comprise both an alkylene group and a dialkyl silyl group, such as xe2x80x94(CH2)txe2x80x94Si(CH3)2xe2x80x94 or xe2x80x94Si(CH3)2xe2x80x94(CH2)txe2x80x94 wherein t is an integer of from 1 to about 10.
The terminal groups on the block copolymer are bonded to the A and Axe2x80x2 blocks in an ABCBxe2x80x2Axe2x80x2 block copolymer and are bonded to the B and Bxe2x80x2 blocks in a BACAxe2x80x2Bxe2x80x2 block copolymer, and typically are hydrogen atoms, hydroxyl groups, alkyl groups, hydroxyl-substituted alkyl groups, or alkoxy groups, wherein the alkyl, hydroxyl-substituted alkyl, and alkoxy groups typically have from 1 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range, and although other terminal groups can be selected. Preferably the terminal group is selected to avoid a peroxy linkage; accordingly, if the atom of the block immediately connected to the terminal group is an oxygen atom, terminal groups such as hydroxy groups or alkoxy groups preferably are not selected to avoid peroxy linkages.
Suitable block copolymers for the inks of the present invention (also showing the optional spacer groups) include those of the general formulae 
wherein R and Rxe2x80x2 each, independently of the other, are hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R1 and R2 each, independently of the other, is a hydrogen atom, an alkyl group, typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, or an aryl group, typically with from 6 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range, i, z, p, and l are each integers representing the numbers of repeat alkylene oxide monomer units, wherein i, z, p, and l are each, independently of the other, typically from 1 to about 10,000, although the values of i, z, p, and l can be outside of this range, y is an integer representing the number of repeat siloxane monomer units, being typically from 1 to about 5,000, although the value of y can be outside of this range, and S and Sxe2x80x2 are optional spacer groups.
Specific examples of block copolymers suitable for the inks of the present invention include those of Formula 1 (which have no spacer groups): 
those of Formula 2 (which have no spacer groups): 
those of Formula 3 (which have spacer groups): 
and those of Formula 4 (which have spacer groups): 
wherein R and Rxe2x80x2 each, independently of the other, are hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R1 and R2 each, independently of the other, is a hydrogen atom, an alkyl group, typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, or an aryl group, typically with from 6 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range, i, z, p, and l are each integers representing the numbers of repeat alkylene oxide monomer units, wherein i, z, p, and l are each, independently of the other, typically from 1 to about 10,000, although the values of x, y, m, and n can be outside of this range, y is an integer representing the number of repeat siloxane monomer units, being typically from 1 to about 5,000, although the value of y can be outside of this range, and j and k are each integers representing the number of repeat xe2x80x94(CH2)xe2x80x94 units, being typically of from 0 to about 10, although the values of j and k can be outside of this range, wherein j+kxe2x89xa71.
An example of a material of Formula 1 is that of Formula 1A, wherein R is selected to be a hydroxyl group and Rxe2x80x2 is selected to be a hydrogen atom, so that the block copolymer has two terminal hydroxyl groups (which can also be described as terminal hydroxypropoxylate groups): 
wherein i, z, y, p, l, R1, and R2 are as defined hereinabove for block copolymers of Formula 1. An example of a material of Formula 1A is that wherein R1 and R2 are each selected to be methyl and i and l are each selected to be 1, a material of Formula 1A(1): 
wherein z, y, and p are as defined hereinabove for block copolymers of Formula 1. This material, which can be called poly(dimethylsiloxane), ethoxylated, hydroxypropoxylate end-capped, is available from Aldrich Chemical Co., Milwaukee, Wis. as Catalog No. 48,271-4, Chemical Abstracts Service Registry No. 68037-63-8.
An example of a material of Formula 2 is that of Formula 2A, wherein R is selected to be a hydroxyl group and Rxe2x80x2 is selected to be a hydrogen atom, so that the block copolymer has two terminal hydroxyl groups (which can also be described as terminal hydroxyethoxylate groups): 
wherein z, i, y, l, p, R1, and R2 are as defined hereinabove for polymers of Formula 2. An example of a material of Formula 2A is that wherein R1 and R2 are each selected to be methyl and z and p are each selected to be 1, a material of Formula 2A(1): 
wherein i, y, and l are as defined hereinabove for polymers of Formula 2. This material can be called poly(dimethylsiloxane), propoxylated, hydroxyethoxylate end-capped.
An example of a material of Formula 3 is that of Formula 3A, wherein R is selected to be a hydroxyl group and Rxe2x80x2 is selected to be a hydrogen atom, so that the block copolymer has two terminal hydroxyl groups (which can also be described as terminal hydroxypropoxylate groups): 
wherein i, z, j, y, k, p, l, R1, and R2 are as defined hereinabove for polymers of Formula 3. An example of a material of Formula 3A is that wherein R1 and R2 are each selected to be methyl, j and k are each selected to be 3, and i and l are each selected to be 1, a material of Formula 3A(1): 
wherein z, y, and p are as defined hereinabove for polymers of Formula 3. This material can be called poly(dimethylsiloxane), propylene ethoxylated, hydroxypropoxylate end-capped.
An example of a material of Formula 4 is that of Formula 4A, wherein R is selected to be a hydroxyl group and Rxe2x80x2 is selected to be a hydrogen atom, so that the block copolymer has two terminal hydroxyl groups (which can also be described as terminal hydroxyethoxylate groups): 
wherein z, i, j, y, k, l, p, R1, and R2 are as defined hereinabove for block copolymers of Formula 4. An example of a material of Formula 4A is that wherein R1 and R2 are each selected to be methyl, j and k are each selected to be 3, and z and p are each selected to be 1, a material of Formula 4A(1): 
wherein i, y, and l are as defined hereinabove for block copolymers of Formula 4. This material can be called poly(dimethylsiloxane), propylene propoxylated, hydroxyethoxylate end-capped.
For illustration purposes, further examples of suitable ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 and BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymers for the inks of the present invention will now be presented. Type A block copolymers (those of Formula I and Formula II) have a C block with one or more alkylsiloxane or dialkylsiloxane repeat monomer units, wherein the alkyl groups of the alkylsiloxane or dialkylsiloxane each, independently of the other, have from 1 to about 10 carbon atoms. Type A materials include, but are not limited to, the following: 
wherein R and Rxe2x80x2 each, independently of the other, can be hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R1 and R2 each, independently of the other, are hydrogen atoms or alkyl groups (including linear, branched, and cyclic alkyl groups) typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, either (a) R3 and R4 are ethylene oxide groups and R5 and R6 are propylene oxide groups or (b) R3 and R4 are propylene oxide groups and R5 and R6 are ethylene oxide groups, v, g, h, and u are each, independently of the others, integers representing the number of repeat alkylene oxide groups, and typically are from 1 to about 10,000, and y is an integer representing the number of alkylsiloxane or dialkylsiloxane repeat groups, and typically is from 1 to about 5,000. In the block copolymers of Formula I, one spacer group is an alkylsiloxy or dialkylsiloxy group and one spacer group is an alkylsilyl or dialkylsilyl group. The following types of linkages between the spacer groups and the alkylene oxide groups are possible: 
(wherein n is 2 in the case of ethylene oxide groups and 3 in the case of propylene oxide groups).
For example, when R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can be of Formula IA:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IA 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si (CH3)2O)yxe2x80x94Si (CH3)2xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IAxe2x80x2:
Rxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IAxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3Cxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
xe2x80x83HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IB:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IB 
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can be of Formula IC:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IC 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
xe2x80x83Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94H
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula ICxe2x80x2:
Rxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83ICxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3COxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula ID:
xe2x80x83Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83ID
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
Type A materials also include, but are not limited to, the following: 
wherein R and Rxe2x80x2 each, independently of the other, can be hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R1 and R2 each, independently of the other, are hydrogen atoms or alkyl groups (including linear, branched, and cyclic alkyl groups) typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, either (a) R3 and R4 are ethylene oxide groups and R5 and R6 are propylene oxide groups or (b) R3 and R4 are propylene oxide groups and R5 and R6 are ethylene oxide groups, v, g, h, and u are each, independently of the others, integers representing the number of repeat alkylene oxide groups, and typically are from 1 to about 10,000, y is an integer representing the number of alkylsiloxane or dialkylsiloxane repeat groups, and typically is from 1 to about 5,000, and a and b each, independently of the other, are integers of from 0 to about 10, wherein the sum of a+bxe2x89xa71. In the block copolymers of Formula II, one spacer group is a combination of an alkylene group and an alkylsiloxy or dialkylsiloxy group and one spacer group is a combination of an alkylene group and an alkylsilyl or dialkylsilyl group. The following types of linkages between the spacer groups and the alkylene oxide groups are possible: 
(wherein n is 2 in the case of ethylene oxide groups and 3 in the case of propylene oxide groups).
For example, when R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can be of Formula IIA:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIA 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IIAxe2x80x2:
Rxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIAxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3Cxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IIB:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIB 
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can be of Formula IIC:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIC 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IICxe2x80x2:
Rxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IICxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3COxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R1 and R2 are selected as methyl groups, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IID:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IID 
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
Type B block copolymers (those of Formula III and Formula IV) have a C block with one or more alkylarylsiloxane repeat monomer units, wherein the alkyl group of the alkylarylsiloxane has from 1 to about 10 carbon atoms and the aryl group of the alkylarylsiloxane has from 6 to about 20 carbon atoms. Type B materials include, but are not limited to, the following: 
wherein R and Rxe2x80x2 each, independently of the other, can be hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 20 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R7 is an alkyl group (including linear, branched, and cyclic alkyl groups) typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, R8 is an aryl group, typically with from 6 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range, either (a) R3 and R4 are ethylene oxide groups and R5 and R6 are propylene oxide groups or (b) R3 and R4 are propylene oxide groups and R5 and R6 are ethylene oxide groups, v, g, h, and u are each, independently of the others, integers representing the number of repeat alkylene oxide groups, and typically are from 1 to about 10,000, and y is an integer representing the number of alkylarylsiloxane repeat groups, and typically is from 1 to about 5,000. In the block copolymers of Formula III, one spacer group is an alkylarylsiloxy group and one spacer group is an alkylarylsilyl group. The following types of linkages between the spacer groups and the alkylene oxide groups are possible: 
(wherein n is 2 in the case of ethylene oxide groups and 3 in the case of propylene oxide groups).
For example, when R7 is selected as a methyl group and R8 is selected as a phenyl group (xcfx86), R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can be of Formula IIIA:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIIA 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
xe2x80x83Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C2H4O)hxe2x80x94)C3H6O)uxe2x80x94H
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IIIAxe2x80x2:
Rxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIIAxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3COxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R2 is selected as a phenyl group, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IIIB:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si (CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can be of Formula IIIC:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIIC 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(C3H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IIICxe2x80x2:
Rxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIICxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)h(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3COxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IIID:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IIID 
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)ySi(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
Type B materials also include, but are not limited to, the following: 
wherein R and Rxe2x80x2 each, independently of the other, can be hydrogen atoms, hydroxyl groups, alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 20 carbon atoms, although the number of carbon atoms can be outside of these ranges, hydroxyl-substituted alkyl groups (including linear, branched, and cyclic alkyl groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, or alkoxy groups (including linear, branched, and cyclic alkoxy groups), typically with from 1 to about 30 carbon atoms, although the number of carbon atoms can be outside of these ranges, R7 is an alkyl group (including linear, branched, and cyclic alkyl groups) typically with from 1 to about 10 carbon atoms, although the number of carbon atoms can be outside of this range, R8 is an aryl group, typically with from 6 to about 20 carbon atoms, although the number of carbon atoms can be outside of this range, either (a) R3 and R4 are ethylene oxide groups and R5 and R6 are propylene oxide groups or (b) R3 and R4 are propylene oxide groups and R5 and R6 are ethylene oxide groups, v, g, h, and u are each, independently of the others, integers representing the number of repeat alkylene oxide groups, and typically are from 1 to about 10,000, y is an integer representing the number of dialkylsiloxane repeat groups, and typically is from 1 to about 5,000, and a and b each, independently of the other, are integers of from 0 to about 10, wherein the sum of a+bxe2x89xa71. In the polymers of Formula IV, one spacer group is a combination of an alkylene group and an alkylarylsiloxy group and one spacer group is a combination of an alkylene group and an alkylarylsilyl group. The following types of linkages between the spacer groups and the alkylene oxide groups are possible: 
(wherein n is 2 in the case of ethylene oxide groups and 3 in the case of propylene oxide groups).
For example, when R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can be of Formula IVA:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVA 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6
O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86) xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)a
xe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(C2H4O)hxe2x80x94(C3H6
O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R7 is selected as a methyl group and R8 selected as a phenyl group, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IVAxe2x80x2:
Rxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6) 
uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVAxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6) 
uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
xe2x80x83H3COxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)a
xe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2) 
bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C3H6O)vxe2x80x94(C2H4O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)ySi(CH3)(xcfx86) xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as propylene oxide groups, and R5 and R6 are selected as ethylene oxide groups, the block copolymer can also be of Formula IVB:
Rxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86) xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVB 
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86) xe2x80x94(CH2)bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)
bxe2x80x94(OC2H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3) 
(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC2
H4)hxe2x80x94(OC3H6)uxe2x80x94OCH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC3H6)vxe2x80x94(OC2H4)gxe2x80x94(CH2)axe2x80x94Si(CH3) 
(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC2H4) 
hxe2x80x94(OC3H6)uxe2x80x94OH 
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can be of Formula IVC:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3) 
(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(C3
H6O)hxe2x80x94(C2H4O)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVC 
When R and Rxe2x80x2 are both hydrogen atoms, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3) 
(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(C3
H6O)hxe2x80x94(C2H4O)uxe2x80x94H 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methyl groups, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)
(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(C3
H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)
(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3) 
(xcfx86)xe2x80x94(CH2)bxe2x80x94(C3
H6O)hxe2x80x94(C2H4O)uxe2x80x94CH3 
which has one terminal hydroxyl group and one terminal methoxy group. When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IVCxe2x80x2:
Rxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86) xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVCxe2x80x2
When R and Rxe2x80x2 are both hydroxyl groups, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R and Rxe2x80x2 are both methoxy groups, the material is of the formula
H3COxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)aSi(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3 
which has two terminal methoxy groups. When R is a hydroxyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
HOxe2x80x94(C2H4O)vxe2x80x94(C3H6O)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3
which has one terminal hydroxyl group and one terminal methoxy group.
When R7 is selected as a methyl group and R8 is selected as a phenyl group, R3 and R4 are selected as ethylene oxide groups, and R5 and R6 are selected as propylene oxide groups, the block copolymer can also be of Formula IVD:
Rxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)ySi(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94Rxe2x80x2xe2x80x83xe2x80x83IVD
When R is a hydrogen atom and Rxe2x80x2 is a hydroxyl group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH 
which has two terminal hydroxyl groups. When R is a methyl group and Rxe2x80x2 is a methoxy group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3
which has two terminal methoxy groups. When R is a hydrogen atom and Rxe2x80x2 is a methoxy group, the material is of the formula
Hxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)yxe2x80x94Si(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OCH3
which has one terminal hydroxyl group and one terminal methoxy group. When R is a methyl group and Rxe2x80x2 is a hydroxyl group, the material is of the formula
H3Cxe2x80x94(OC2H4)vxe2x80x94(OC3H6)gxe2x80x94(CH2)axe2x80x94Si(CH3)(xcfx86)Oxe2x80x94(Si(CH3)(xcfx86)O)ySi(CH3)(xcfx86)xe2x80x94(CH2)bxe2x80x94(OC3H6)hxe2x80x94(OC2H4)uxe2x80x94OH
which has one terminal hydroxyl group and one terminal methoxy group.
ABCBA and BACAB copolymers suitable for the inks of the present invention can be obtained commercially from, for example, Aldrich Chemical Co., Milwaukee, Wis.
In addition, alkylene oxide/siloxane copolymers suitable for the inks of the present invention can be obtained by the reaction of a hydride terminated polydialkyl siloxane (for example, polydimethylsiloxane, Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H) with polyols (xe2x80x94OH containing groups) containing polyethyleneoxide units, polypropyleneoxide units, or a mixture thereof in the presence of metal catalyst (for example, zinc chlorides, zinc acetates, zinc octoates, iron chlorides, iron acetates, iron octoates, tin chlorides, tin acetates, tin octoates, platinum complexes, dibutyl tin dilaurate, tributyl tin oxide, dibutyl acetoxytin, Pd/C, or the like).
Further, alkylene oxide/siloxane copolymers suitable for the inks of the present invention can be obtained by the reaction of a hydride terminated polydialkyl siloxane (for example, polydimethylsiloxane, Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H) with vinyl or allyl ethers of polyols (containing one xe2x80x94OH group or one ether group), including those materials containing polyethyleneoxide units, polypropyleneoxide units, or a mixture thereof in the presence of a metal catalyst (for example, zinc chlorides, zinc acetates, zinc octoates, iron chlorides, iron acetates, iron octoates, tin chlorides, tin acetates, tin octoates, platinum complexes, dibutyl tin dilaurate, tributyl tin oxide, dibutyl acetoxytin, Pd/C, or the like).
Exemplary reactions (each taking place in the presence of one or more metal catalysts) are as follows:
Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H+HOxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Rxe2x86x92ROxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94R+2H2Hxe2x80x94Si(CH3)2xe2x80x94O(Si(CH3)2xe2x80x94O) Oxe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Rxe2x80x2+2H2Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H+HOxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Rxe2x86x92ROxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)exe2x80x94Si(CH3)2H+HOxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Rxe2x86x92ROxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94R+2H24Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H+4HOxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94R+4HOxe2x80x94(C3H6O)fxe2x80x94(C2H4O)exe2x80x94Rxe2x80x2xe2x86x92ROxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94R+Rxe2x80x2Oxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Rxe2x80x2+Rxe2x80x2Oxe2x80x94(C3H4HOxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Rxe2x80x2+4HOxe2x80x94(C2H4O)exe2x80x94Rxe2x86x92ROxe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94R+Rxe2x80x2Oxe2x80x94(C
wherein R, Rxe2x80x2 and y are as defined hereinabove with respect to Formulae 1, 2, 3, and 4, and e=i=l and f=z=p wherein i, l, z, and p are as defined hereinabove with respect to Formulae 1, 2, 3, and 4.
The following reactions (either with or without metal catalysts) can also be used to prepare block copolymers for inks of the present invention:
xe2x89xa1SiOH+HO(C2H4O)fHxe2x86x92xe2x89xa1Sixe2x80x94Oxe2x80x94(C2H4O)fH 
xe2x89xa1SiOH+HO(C3H6O)gHxe2x86x92xe2x89xa1Sixe2x80x94Oxe2x80x94(C3H6O)gH 
xe2x89xa1SiH+HO(C2H4O)fHxe2x86x92xe2x89xa1Sixe2x80x94(C2H4O)fH 
xe2x89xa1SiH+HO(C3H6O)gHxe2x86x92xe2x89xa1Sixe2x80x94(C3H6O)gH 
xe2x89xa1SiH+CH2xe2x95x90CH2xe2x80x94CH2xe2x80x94(OC2H4O)f
H(+catalyst)xe2x86x92xe2x89xa1Sixe2x80x94(CH2)3xe2x80x94(OC2H4)fOH 
xe2x89xa1SiH+CH2xe2x95x90CH2xe2x80x94CH2xe2x80x94(OC3H6O)g
H(+catalyst)xe2x86x92xe2x89xa1Sixe2x80x94(CH2)3xe2x80x94(OC3H6)gOH 
wherein f and g are each independently integers of from 1 to about 15,000.
Alkylene oxide/siloxane copolymers suitable for the inks of the present invention can also be obtained by the reaction of a polydimethylsiloxane comprising two active terminal xe2x89xa1SiH groups (Hxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2H) with corresponding vinyl or ally group containing polyethyleneoxide, polypropyleneoxide, or a mixture thereof in the presence of a metal catalyst.
Alkylene oxide/siloxane block copolymers suitable for the inks of the present invention can also be obtained by the following reactions with vinyl or allyl compounds in the presence of a metal catalyst:
Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H+2CH2xe2x95x90CHxe2x80x94(CH2) r-2xe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Rxe2x80x2xe2x86x92Rxe2x80x2xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94(CH2)r-2xe2x80x94CH2CH2xe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94CH2CH2xe2x80x94(CH2)r-2xe2x80x94(C2Hxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2H+2CH2xe2x95x90CHxe2x80x94(CH2) r-2xe2x80x94(C3H6O)6xe2x80x94(C2H4O) fxe2x80x94Rxe2x86x92Rxe2x80x94(C2H4O)exe2x80x94(C3H6O)fxe2x80x94(CH2)r-2xe2x80x94CH2CH2xe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2xe2x80x94CH2CH2xe2x80x94(CH2)r-2xe2x80x94(C3H6Hxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2H+2CH2xe2x95x90CHxe2x80x94CH2xe2x80x94(CH2)r-3xe2x80x94(C2H4O)fxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Rxe2x80x2xe2x86x92Rxe2x80x2(C3H6O)e(C2H4O)f(CH2)r-3CH2CH2CH2Si(CH3)2O(Si(CH3)2O)ySi(CH3)2xe2x80x94CH2CH2CH2(CH2 
which can also be written as
Rxe2x80x2xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94(CH2)sxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)sxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94Rxe2x80x2Hxe2x80x94Si(CH3)2Oxe2x80x94(Si(CH3)2O)yxe2x80x94Si(CH3)2H+2CH2xe2x95x90CHxe2x80x94CH2xe2x80x94(CH2)r-3xe2x80x94(C3H6O)exe2x80x94(C2H4O)fxe2x80x94Rxe2x86x92R(C2H4O)f(C3H6O)e(CH2)r-3CH2CH2CH2Si(CH3)2O(Si(CH3)2O)ySi(CH3)2xe2x80x94CH2CH2CH2(CH2)r-3(C3H6O)e 
which can also be written as
Rxe2x80x94(C2H4O)fxe2x80x94(C3H6O)exe2x80x94(CH2)sxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94(Si(CH3)2xe2x80x94O)yxe2x80x94Si(CH3)2xe2x80x94(CH2)sxe2x80x94(C3H6O)exe2x80x94(C2H4O)f xe2x80x94R 
wherein R, Rxe2x80x2 and y are as defined hereinabove with respect to Formulae 1, 2, 3, and 4, and e=i=l and f=z=p wherein i, l, z, and p are as defined hereinabove with respect to Formulae 1, 2, 3, and 4, and r and s are integers.
The coupling reaction of a hydropolysiloxane derivative (containing xe2x89xa1SiH) and a hydroxyl active material (HOR) such as polyethylene glycol, polypropylene glycol, mixed polyethyleneglycol and polypropylene glycol, alkyl ethers of polyethylene glycol, alkyl ethers of polypropylene glycol, alkyl ethers of mixed polyethyleneglycol and polypropylene glycol, or the like in the presence of a metal catalyst is known. The coupling reaction of a polydimethylsiloxane derivative comprising two active terminal xe2x89xa1SiH groups and an unsaturated material (with a double bond, such as vinyl or ally group containing polyethyleneoxide, polypropyleneoxide, or mixture thereof) in the presence of a metal catalyst is also known. Additional synthetic methods for the preparation of ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 and BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymers for the inks of the present invention are disclosed in, for example, Silicon Compounds: Register and Review (5th Edition), published by United Chemical Technologies, Inc. (Formally Hxc3xcls America, Inc. or Petrarch Systems, Inc., Bartram Road, Bristol, Pa. 19007), the disclosure of which is totally incorporated herein by reference.
The ABCBA or BACAB block copolymer is present in the ink of the present invention in any desired or effective amount, typically at least about 0.001 percent by weight of the ink, preferably at least about 0.005 percent by weight of the ink, and more preferably at least about 0.01 percent by weight of the ink, and typically no more than about 8 percent by weight of the ink, preferably no more than about 5 percent by weight of the ink, and more preferably no more than about 4 percent by weight of the ink, although the amount can be outside of these ranges.
The inks of the present invention can optionally include a jetting aid such as polyethylene oxide (typically in amounts of less than about 5 percent by weight) or a small quantity (typically less than about 0.2 percent by weight) of stabilized pigment particles. A preferred polyethylene oxide is one having a weight average molecular weight of about 18,500, although the molecular weight of the jetting aid can be different. Examples of inks containing preferred polyethylene oxides are disclosed in, for example, U.S. Pat. No. 5,207,825, the disclosure of which is totally incorporated herein by reference. The jetting aid provides smooth jetting or jetting with low jitter.
Other desired additives, including water soluble polymers, pH buffering agents, biocides, chelating agents (EDTA and the like), anticurl agents, antibleed agents, and other known ink additives can also optionally be used in the inks of the present invention. Such additives can generally be added to the inks in known amounts for their known purposes.
Additives such as surfactants (or wetting agents), anti-curl agents, anti-intercolor bleed agents, and anticlogging agents can also be added to the inks of the present invention. Some of these surfactants can be of the anionic, cationic, or nonionic types. Suitable surfactants and wetting agents include, but are not limited to, Tamol SN(copyright), Tamol LG(copyright), and Triton(copyright) series (Rohm and Haas Co.); Marasperse(copyright) series; Igepal(copyright) series (Rhone-Poulenc Co., formerly from GAF Co.); Tergitol(copyright) series; Duponol(copyright) series (E. I. Du Pont de Nemours and Co.); Surfynol Series (Air Products Inc.); Iconol(copyright) Series (BASF Co.); Brij(copyright) Series (ICI Americas Inc.); Pluronic(copyright) Series (BASF Co.); Emulphor(copyright) ON 870 and ON 877 (GAF); and other commercially available surfactants. These surfactants (or dispersants) and wetting agents can be present in the ink in effective amounts, generally from 0 to about 15 percent by weight of the ink, preferably from about 0.001 to about 10 percent by weight of the ink, and more preferably from about 0.01 to about 8 percent by weight of the ink, although the amount can be outside of these ranges.
Polymeric additives can also be added to the inks for the present invention to enhance the viscosity or smear resistance of the ink. Suitable polymeric additives include, but are not limited to, water soluble polymers and random copolymers such as Gum Arabic, salts, polyvinyl alcohols, polyvinyl sulfonate salts, polyhydroxypropylcellulose, polyhydroxyethylcellulose, polyvinylpyrrolidinone, polyvinylether, starch, polysaccharides, carboxymethylcellulose salts, polyethyleneimines derivatized with ethylene oxide and/or propylene oxide, such as the Discole(copyright) series (DKS International); the Jeffamine(copyright) series (Texaco); and the like as well as mixtures thereof. Polymeric additives can be present in the ink in amounts of from 0 to about 10 percent by weight of the ink, preferably from about 0.001 to about 8 percent by weight of the ink, and more preferably from about 0.01 to about 5 percent by weight of the ink, although the amount can be outside of these ranges.
Other optional additives include, but are not limited to, biocides such as Dowicil(copyright) 150, 200, and 75, benzoate salts, sorbate salts, Proxcel(copyright) (available from ICI), and the like. When used, such biocides are generally present in an amount of from 0 to about 10 percent by weight of the ink, preferably from about 0.001 to about 8 percent by weight of the ink, and more preferably from about 0.01 to about 4.0 percent by weight of the ink, although the amount can be outside of these ranges. Inks for the present invention can also include pH controlling (buffering) agents. Suitable pH controlling agents or buffering agents include, but are not limited to, acids, bases, phosphate salts, carboxylate salts, sulfite salts, sulfate salts, amine salts, and the like. Such pH controlling agents (buffering agents) are generally present in an amount of from 0 to about 10 percent by weight of the ink, preferably from about 0.001 to about 7.5 percent by weight of the ink, and more preferably from about 0.01 to about 5 percent by weight of the ink, although the amount can be outside of these ranges.
The ink compositions can be of any desired or suitable viscosity. For thermal ink jet printing applications, for example, the viscosity can be up to about 25 centipoise at about 25xc2x0 C., preferably being below about 10 centipoise at about 25xc2x0 C., and more preferably being below about 5 centipoise at about 25xc2x0 C., although the viscosity can be outside these ranges, particularly for applications other than thermal ink jet printing, such as acoustic ink jet printing or the like.
Inks of the present invention exhibit fast drying rates, low intercolor bleed, and reduced mottle and smearing. While not being limited to any particular theory, it is believed that the inks of the present invention have low surface tension that allows them to penetrate faster into printed substrate, thus preventing intercolor bleed. Printing a low surface tension ink (such as a color ink) underneath a high surface tension ink (such as a black ink) can also enhance the drying rate of the black ink and reduce its intercolor bleed with the neighboring color ink. The ink comprising the BASCSxe2x80x2Axe2x80x2Bxe2x80x2 or ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 block copolymer of the present invention can also provide a hydrophobic layer near the border area next to its adjacent ink, thereby inhibiting intercolor bleed. In addition, since the inks of the present invention do not react with many common ink jet ingredients, they can be used in conjunction with many other ink compositions in a single partitioned printhead without resulting in undesired ink mixing, colorant precipitation, or printhead clogging. The inks of the present invention can have low surface tension and can exhibit decreased dry time on print substrates. The inks of the present invention can also be printed under or above another ink to enhance the drying rate of the other ink.
The present invention is also directed to a process which entails incorporating an ink composition of the present invention into an ink jet printing apparatus and causing droplets of the ink composition to be ejected in an imagewise pattern onto a print substrate. In one particularly preferred embodiment, the printing apparatus employs a thermal ink jet process wherein the ink in the nozzles is selectively heated in an imagewise pattern according to digital signals, thereby causing droplets of the ink to be ejected in imagewise pattern onto the print substrate. In another embodiment, the printing apparatus employs an acoustic ink jet process wherein droplets of the ink are ejected in imagewise pattern onto the print substrate by acoustic beams according to electronic signals. Optionally, the print substrate can be heated by any desired heating means at any stage of the ink jet printing process, including before printing, during printing, after printing, or combinations thereof.
The print substrate employed can be any substrate compatible with aqueous inks. Suitable substrates include, but are not limited to, textiles; plain papers, such as Xerox(copyright) series 10, Xerox(copyright) 4024, Xerox(copyright) Digital Paper, Xerox(copyright) Image Series LX Paper, Hewlett-Packard(copyright) BrightWhite Ink Jet plain paper, Georgia Pacific(copyright) Microprint Ink Jet paper 24 lb, Xerox(copyright) 4200 DP paper, Rank Xerox(copyright) Plain Paper, Japanese Hokuetsu L Plain Paper, Fuji Xerox(copyright) Kakusaku L paper, various Japanese plain papers, Strathmore(copyright) Legacy paper, Ampad(copyright) Premium grade paper, Hammermill(copyright) Jet Print paper, Hammermill(copyright) Tidal DP paper, GP Microprint paper, Weyerhaeuser(copyright) Jet-Xtra paper, Boise(copyright) Cascade paper, Union Camp(copyright) Great White Recycled paper, Union Camp(copyright) Top Gun ink jet paper, Champion(copyright) paper, commercial bond papers and the like; coated papers (or special ink jet papers including photo-realistic ink jet papers) such as those available from Hewlett-Packard, Canon, Eastman Kodak, Oji Paper, 3M, Mitsubishi, Polaroid, Lexmark, Epson, and Xerox; ink jet transparencies suitable for aqueous inks or ink jet printing processes, including those from Arkwright, Hewlett-Packard, Canon, Asahi, Lexmark, Epson, Eastman Kodak, Polaroid, and Xerox; and the like, as well as materials from other commercial sources.
Another embodiment of the present invention is directed to a set of inks for printing multicolor images in an ink jet printer, said ink set comprising (1) a first ink having a first color and comprising water and a first colorant; and (2) a second ink having a second color different from the first color and comprising water, a second colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of a dialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the first ink and the second ink are printed adjacent to each other on a print substrate. Yet another embodiment of the present invention is directed to a multicolor ink jet printing process which comprises: (1) incorporating into an ink jet printer a first ink having a first color and comprising water and a first colorant; (2) incorporating into the ink jet printer a second ink having a second color different from the first color and comprising water, a second colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of a dialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block; (3) causing droplets of the first ink to be ejected in an imagewise pattern onto a substrate; and (4) causing droplets of the second ink to be ejected in an imagewise pattern onto the substrate, wherein dry time of the ink containing the block copolymer is decreased and/or intercolor bleed between the first ink and the second ink is reduced when the first ink and the second ink are printed adjacent to each other on the substrate. Still another embodiment of the present invention is directed to a multicolor ink jet printing process which comprises: (1) incorporating into an ink jet printer a first ink having a first color and comprising water and a first colorant; (2) incorporating into the ink jet printer a second ink having a second color different from the first color and comprising water, a second colorant, and an ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer wherein A and Axe2x80x2 are blocks containing one or more ethylene oxide repeat monomer units, B and Bxe2x80x2 are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of a dialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and Sxe2x80x2 is an optional spacer group between the C block and the Axe2x80x2 or Bxe2x80x2 block; (3) causing droplets of the first ink to be ejected in an imagewise pattern onto a substrate; and (4) causing droplets of the second ink to be ejected in an imagewise pattern onto the substrate, wherein dry time of the first ink is reduced when the second ink is printed either above or below the first ink. It is believed that the dry time of the first ink can be reduced by the priming action of the second ink, which can have reduced surface tension.
In a multicolor printing process, any ink printing order (such as (1) black, cyan, magenta, yellow, (2) yellow, cyan, magenta, black, (3) yellow, magenta, cyan, black, (4) black, magenta, yellow, cyan, or the like can be used in the printing process. In particular, the ink containing the ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer can be printed onto the substrate either before or after the ink that contains no ABSCSxe2x80x2Bxe2x80x2Axe2x80x2 or BASCSxe2x80x2Axe2x80x2Bxe2x80x2 block copolymer.
Specific embodiments of the invention will now be described in detail. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated.